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United States Patent |
5,194,472
|
Wilson
,   et al.
|
March 16, 1993
|
Ester-containing quaternary ammonium salts as adhesion improving toner
charge agents
Abstract
Toner particles comprising a polyester binder and a charge control agent
are provided wherein such agent is a quaternary ammonium salt having one
or more ester-containing moieties. Such an ester-containing salt causes
toner particles to display lower fusing temperature, improved paper
adhesion indexes, and improved polyester binder compatibility compared to
nonesterified salts.
Inventors:
|
Wilson; John C. (Rochester, NY);
DeMejo; Lawrence P. (Rochester, NY);
Bermel; Alexandra D. (Spencerport, NY)
|
Assignee:
|
Eastman Kodak Company (Rochester, NY)
|
Appl. No.:
|
873303 |
Filed:
|
April 24, 1992 |
Current U.S. Class: |
524/238; 430/104; 430/105; 430/108.2; 430/108.21; 554/91; 554/103; 554/110; 560/1; 560/7; 560/61; 560/110; 564/282; 564/283; 564/284 |
Intern'l Class: |
C07C 069/75; C07C 069/76; G03G 009/06; G03G 009/08 |
Field of Search: |
524/238
560/1,110,7,61
564/282,283,284
430/106,107,108,110
|
References Cited
U.S. Patent Documents
5110977 | May., 1992 | Wilson | 560/1.
|
Primary Examiner: Schofer; Joseph L.
Assistant Examiner: Zitomer; Fred
Attorney, Agent or Firm: Dressler, Goldsmith, Shore, Sutker & Milnamow Ltd.
Parent Case Text
This is a continuation-in-part of allowed U.S. patent application Ser. No.
479,774, filed Feb. 14, 1990, now U.S. Pat. No. 5,110,977. The teachings
of Ser. No. 479,774 are herein incorporated in their entirety.
Claims
What is claimed is:
1. A quaternary salt of the formula:
##STR34##
wherein R.sub.1 is methyl, cyclohexyl, phenyl, or
4-[2-(N-benzyl-N,N-dimethylammonium)ethoxycarbonyl]phenyl associated with
one of m-nitrobenzenesulfonate and tetraphenylborate, or
4-[2-(N-(2-benzoyloxy)ethyl)-N,N-dimethylammonium)ethoxycarbonyl]phenyl
associated with one of m-nitrobenzenesulfonate and tetraphenylborate;
R.sub.3 is C.sub.1 -C.sub.18 alkyl, benzyl, 2-(cyclohexanoyloxy)ethyl or
2-(benzoyloxy)ethyl;
R.sub.4 is methyl or benzyl; and
Z.sup..crclbar. is m-nitrobenzenesulfonate or tetraphenylborate;
provided that R.sub.1 is not cyclohexyl or phenyl when R.sub.3 is methyl,
R.sub.4 is benzyl, and Z.sup..crclbar. is m-nitrobenzenesulfonate.
2. A quaternary salt as in claim 1 wherein R.sub.1 is methyl or phenyl;
R.sub.3 is methyl, C.sub.14 -C.sub.18 alkyl, or benzyl; R.sub.4 is methyl;
and Z.sup..crclbar. is m-nitrobenzenesulfonate or tetraphenylborate.
3. A quaternary salt as in claim 1 wherein R.sub.1 is cyclohexyl or phenyl;
R.sub.3 is 2-(cyclohexanoyloxy)ethyl or 2-(benzoyloxy)ethyl; R.sub.4 is
methyl or benzyl; and Z.sup..crclbar. is m-nitrobenzenesulfonate or
tetraphenylborate.
4. A quaternary salt as in claim 1 wherein R.sub.1 is phenyl; R.sub.3 is
normal C.sub.18 alkyl; R.sub.4 is methyl; and Z.sup..crclbar. is
m-nitrobenzenesulfonate or tetraphenylborate.
5. A quaternary salt as in claim 1 wherein R.sub.1 is
4-[2-(N-benzyl-N,N-dimethylammonium)ethoxy-carbonyl]phenyl associated with
one of m-nitrobenzenesulfonate and tetraphenylborate or
4-[2-(N-(2-(benzoyloxy)ethyl)-N,N-dimethylammonium)ethoxycarbonyl]phenyl
associated with one of m-nitrobenzenesulfonate and tetraphenylborate;
R.sub.3 is benzyl or 2-(benzoyloxy)ethyl
R.sub.4 is methyl; and
Z.sup..crclbar. is m-nitrobenzenesulfonate or tetraphenylborate.
6. Toner particles comprising a thermoplastic polymeric matrix phase which
has dispersed therein a quaternary ammonium salt of the formula:
##STR35##
wherein R.sub.1 is alkyl, aryl, or
##STR36##
wherein R.sub.5 is arylene or alkylene; R.sub.2 is alkyl, aryl or aralkyl;
R.sub.3 is alkyl, aryl, aralkyl or
##STR37##
R.sub.4 is alkyl, aryl or aralkyl; X is (CH.sub.2).sub.n or arylene;
Z.sup..crclbar. is an anion; and
n is an integer from 2 to 6.
7. A toner particle as in claim 6 wherein R.sub.1 is methyl or phenyl;
R.sub.3 is methyl, C.sub.14 -C.sub.18 alkyl, or benzyl; R.sub.4 is methyl;
and Z.sup..crclbar. is m-nitrobenzenesulfonate or tetraphenylborate.
8. A toner particle as in claim 6 wherein R.sub.1 is cyclohexyl or phenyl;
R.sub.3 is 2-(cyclohexanoyloxy)ethyl or 2-(benzoyloxy)ethyl; R.sub.4 is
methyl or benzyl; and Z.sup..crclbar. is m-nitrobenzenesulfonate or
tetraphenylborate.
9. A toner particle as in claim 6 wherein R.sub.1 is phenyl; R.sub.3 is
normal C.sub.18 alkyl; R.sub.4 is methyl; and Z.sup..crclbar. is
m-nitrobenzenesulfonate or tetraphenylborate.
10. A toner particle as in claim 6 wherein R.sub.1 is
4-[2-(N-benzyl-N,N-dimethylammonium)ethoxycarbonyl]phenyl associated with
one of m-nitrobenzenesulfonate and tetraphenylborate or
4-[2-(N-(2-(benzoyloxy)ethyl)-N,N-dimethylammonium)ethoxycarbonyl]phenyl
associated with one of m-nitrobenzenesulfonate and tetraphenylborate;
R.sub.3 is benzyl or 2-(benzoyloxy)ethyl
R.sub.4 is methyl; and
Z.sup..crclbar. is m-nitrobenzenesulfonate or tetraphenylborate.
Description
FIELD OF THE INVENTION
This invention is in the field of ester containing quaternary ammonium
salts having utility as charge control agents for toners that also serve
as adhesion promoters between toner and receiver sheets and as toner
fusing temperature reducers.
BACKGROUND OF THE INVENTION
In the art of making and using toner powders, charge control agents are
commonly employed to adjust and regulate the triboelectric charging
capacity and/or the electrical conductivity characteristics thereof. Many
different charge control agents are known which have been incorporated
into various binder polymers known for use in toner powders. However, the
need for new and improved toner powders that will perform in new and
improved copying equipment has resulted in continuing research and
development efforts to discover new and improved charge control agents.
Of potential interest are substances which not only serve as toner powder
charge control agents, but also function as agents that provide additional
results or effects. Such multi-functionality not only offers the potential
for achieving cost savings in the manufacture and use of toner powders but
also offers the potential for achieving toner powders with performance
capabilities not heretofore known.
Charge control agents that contain either incorporated ester groups or
incorporated quaternary ammonium salt groups are known ("Research
Disclosure No. 21030" Volume 250, October, 1981, published by Industrial
Opportunities, Ltd., Homerville, Havant, Hampshire, P091EF, United
Kingdom) but charge control agents that contain both ester groups and
quaternary ammonium groups in the same molecule are unknown, so far as now
known.
SUMMARY OF THE INVENTION
This invention is directed to toner powders comprising a polymeric matrix
phase which has dispersed therein at least one quaternary ammonium salt
having incorporated therein at least one ester containing moiety that is
bonded through an alkylene linking group to a quaternary ammonium nitrogen
atom.
When incorporated into toner powders, such quaternary ammonium salts not
only function as charge control agents, but also as toner powder fusing
temperature depressants and paper adhesion promoters. These salts are
preferably dispersed in the polymeric binder matrix phase comprising the
core or body portion of a toner particle. These salts appear to have
greater compatibility with polyester resins than prior art charge control
agents that contain only an ester group or a quaternary ammonium group.
Toner powders containing these salts incorporated into the polymeric binder
thereof can be used for producing developed toned images on a latently
imaged photoconductor element, for transfer of the toned image from the
photoconductor element to a receiver sheet, and for heat fusion of the
toned image on the receiver, while employing processes and processing
conditions heretofore generally known to the art of electrophotography.
Various other advantages, aims, features, purposes, embodiments and the
like associated with the present invention will be apparent to those
skilled in the art from the present specification taken with the
accompanying claims.
DETAILED DESCRIPTION
(A) Definitions
The term "particle size" as used herein, or the term "size", or "sized" as
employed herein in reference to the term "particles", means volume
weighted diameter as measured by conventional diameter measuring devices,
such as a Coulter Multisizer, sold by Coulter, Inc. Mean volume weighted
diameter is the sum of the mass of each particle times the diameter of a
spherical particle of equal mass and density, divided by total particle
mass.
The term "glass transition temperature" or "T.sub.g " as used herein means
the temperature at which a polymer changes from a glassy state to a
rubbery state. This temperature (T.sub.g) can be measured by differential
thermal analysis as disclosed in "Techniques and Methods of Polymer
Evaluation", Vol. 1, Marcel Dekker, Inc., N.Y., 1966.
The term "melting temperature" or "T.sub.m " as used herein means the
temperature at which a polymer changes from a crystalline state to an
amorphous state. This temperature (T.sub.m) can be measured by
differential thermal analysis as disclosed in "Techniques and Methods of
Polymer Evaluation".
The term "onset of fusing temperature" as used herein is relation to a
toner powder means the lowest temperature at which a high density solid
area patch developed with this toner exhibits good adhesion to paper as
determined by the adhesion index and crack width tests. The crack width
test involves fusing a toner patch onto paper, folding the patch and
brushing the loose toner away, and evaluating the width of the crack.
The term "adhesion index" as used herein is a measure of toner adhesion to
paper after the toner has been fused. The adhesion index test involves
adhering a metal block to a toner patch and measuring the energy required
to cause interfacial failure between the toner layer and its contacting
substrate by collision of a pendulum with the metal block. The range of
adhesion index is from 0 units (no adhesion of the toner to the substrate)
to 100 units (excellent adhesion of the toner to the substrate).
The term "ester compatibility" as used herein has reference to the capacity
of a thermoplastic polymer, such as one usable in the manufacture of toner
powders, to blend with an additive material which is an ester group
containing quaternary ammonium salt compound.
(B) Quaternary Ammonium Salts
This invention is directed to quaternary ammonium salts of the formula:
##STR1##
wherein R.sub.1 is alkyl, aryl, and
##STR2##
wherein R.sub.5 is arylene or alkylene; R.sub.2 is alkyl, aryl or aralkyl;
R.sub.3 is alkyl, aryl, aralkyl or
##STR3##
R.sub.4 is alkyl, aryl or aralkyl; X is (CH.sub.2).sub.n or arylene;
Z.sup..crclbar. is an anion; and
n is an integer from 2 to 6.
As used herein, the term "alkyl" includes straight and branched chain alkyl
groups and cycloalkyl groups.
As used herein, the term anion refers to negative ions such as
m-nitrobenzenesulfonate, tosylate, tetraphenylborate, dicyanamide,
chloride, and the like.
As used herein, the term aryl includes phenyl, naphthyl, anthryl and the
like.
As used herein, the term arylene includes phenylene, naphthalene, and the
like.
As used herein, the term aralkyl includes benzyl, naphthylmethyl and the
like.
Alkyl and aryl groups can be unsubstituted or substituted with a variety of
substituents such as alkoxy, halo or other groups.
Presently preferred quaternary ammonium salts are those of the formula:
##STR4##
wherein R.sub.1 is methyl, cyclohexyl, phenyl,
4-[2-(N-benzyl-N,N-dimethylammonium)ethoxycarbonyl]phenyl associated with
one of m-nitrobenzenesulfonate and tetraphenylborate, or
4-[2-(N-(2-(benzoyloxy)ethyl)-N,N-dimethylammonium)ethoxycarbonyl]phenyl
associated with one of m-nitrobenzenesulfonate and tetraphenylborate;
R.sub.3 is C.sub.1 -C.sub.18 alkyl, benzyl, 2-(cyclohexanoyloxy)ethyl, or
2-(benzoyloxy)ethyl;
R.sub.4 is methyl or benzyl; and
Z.sup..crclbar. is m-nitrobenzenesulfonate or tetraphenylborate.
In a preferred form of the invention, R.sub.1 is methyl or phenyl; R.sub.3
is C.sub.1 -C.sub.18 alkyl, or benzyl; R.sub.4 is methyl; and
Z.sup..crclbar. is m-nitrobenzenesulfonate or tetraphenylborate.
In another preferred form of the invention R.sub.1 is cyclohexyl or phenyl;
R.sub.3 is 2-(cyclohexanoyloxy)ethyl or 2-(benzoyloxy)ethyl; R.sub.4 is
methyl or benzyl; and Z.sup..crclbar. is m-nitrobenzenesulfonate or
tetraphenylborate.
In yet another preferred form of the invention R.sub.1 is phenyl; R.sub.3
is normal C.sub.18 alkyl; R.sub.4 is methyl; and Z.sup..crclbar. is
m-nitrobenzenesulfonate or tetraphenylborate.
In a fourth preferred form of the invention, R.sub.1 is
4-[2-(N-benzyl-N,N-dimethylammonium)ethoxycarbonyl]phenyl associated with
one of m-nitrobenzenesulfonate and tetraphenylborate or
4-[2-(N-(2-(benzoyloxy)ethyl)-N,N-dimethylammonium)ethoxycarbonyl]phenyl
associated with one of m-nitrobenzensulfonate and tetraphenylborate;
R.sub.3 is benzyl or 2-(benzoyloxy)ethyl; R.sub.4 is methyl; and
Z.sup..crclbar. is m-nitrobenzenesulfonate or tetraphenylborate.
(C) Synthesis
Compounds in accordance with the present invention can be prepared by any
convenient route. One general route, a first route, is to acylate a
N,N-di(lower alkyl) amino lower alkanol with an acid chloride to produce
the corresponding (N,N-di(lower alkyl)amino) alkyl esters which are
subsequently quaternized with a reactive aliphatic or aromatic halide. The
quaternary ammonium compound is converted to the desired anion by a
metathesis or ion exchange reaction with a reactive alkali metal aryl
sulfonate or other acid salt.
Preferably, the acid chloride is either benzoyl chloride or
cyclohexanecarbonyl chloride, while the hydroxylamine is either
2-(N,N-dimethyl)aminoethanol or N-methyldiethanolamine. In place of the
acid chloride, the corresponding carboxylic acid can be employed.
A preferred procedure for such an ester preparation following the first
route is to prepare a basic aqueous solution of the tertiary amino
alkanol. To this solution is slowly added a solution of the acid chloride
in a water immiscible organic solvent, methylene chloride being presently
preferred. The addition is preferably accompanied by rapid stirring. The
equivalent ratio of aminoalkanol to total added acid chloride is
preferably about 1:1. The ensuing reaction is exothermic, and, after the
reaction is complete, stirring is preferably continued for a time period,
such as at least about 1/4 hour. The organic layer is then separated,
washed with water and dried, preferably over MgSO.sub.4 or the like, and
concentrated. The product is typically an oil which can be purified by
distillation.
One convenient and presently preferred procedure for the preparation of the
quaternary ammonium compound following the first route is to separately
prepare the ester and the quaternizing agent as solutes in the same highly
polar solvent, acetonitrile being one presently particularly preferred
example. The equivalent ratio of tertiary amine compound to the
quaternizing agent is preferably about 1:1. Such a solution is then heated
at reflux for a time in the range of about 1 to about 3 hours. The
reaction mixture is then concentrated by solvent evaporation to yield a
viscous oil or a crystalline solid. The product can be used without
further purification for the next step in the syntheses, or the product
can be purified by recrystallization, for example, from a ketone, such as
2-butanone, or the like, followed by washing and drying.
A second general route for preparing quaternary ammonium salts in
accordance with the present invention is to react an aldehyde with a
glycol to produce a cyclic ether. The cyclic ether is further reacted with
an N-halogenated imide to produce a halogenated ester which undergoes an
alkylation reaction with a tertiary amine to produce a quaternary ammonium
halide. Ion exchange converts the quaternary ammonium halide to a
desirable species, such as a sulfonate or a borate.
The preferred aldehyde for the second route is benzaldehyde, especially
when the glycol is ethylene glycol and the N-halogenated imide is
N-bromosuccinimide. More specifically, 2-phenyl-1,3-dioxolane can be
prepared by mixing benzaldehyde and ethylene glycol in a 1.0 to 1.2 mol
ratio in an organic solvent containing a catalytic amount of an organic
acid, such as p-toluenesulfonic acid. The mixture is heated and allowed to
reflux for about an hour and a half, then treated with potassium
carbonate, filtered, and distilled to produce 2-phenyl-1,3-dioxolane. The
dioxolane is subsequently dissolved in carbon tetrachloride with an
equimolar amount of N-bromosuccinimide and a catalytic amount of benzoyl
peroxide. After heating under reflux conditions for up to 16 hours,
cooling, and filtering, the mixture produces a filtrate that can be
further concentrated to yield an ester, 2-bromoethyl benzoate. The ester
so produced is used as an alkylating agent when reacted with a tertiary
amine yielding a quaternary ammonium salt.
It is also possible to combine the first route and the second route to
produce a third general route for synthesizing chemical compounds. For
example, a tertiary amine produced in accordance with the first route and
containing an ester group can be alkylated with the bromo ester produced
in accordance with the second route.
A convenient and presently preferred procedure for preparing a desired
quaternary ammonium salt from an intermediate quaternary ammonium halide
produced by any of the routes described above is to dissolve an ion
exchange agent in an aqueous solution. To this solution is added a second
aqueous solution containing the intermediate halide. The equivalent ratio
of such intermediate halide to such ion exchange agent should be about
1:1. Typically, a precipitate is formed immediately which is in the form
of an oil. This precipitate is isolated, water washed (preferably with
distilled or deionized water), and then dissolved in a water immiscible
organic solvent, such as methylene chloride, or the like. The water layer
is separated, the organic layer is dried over MgSO.sub.4, or the like, and
the product thereby concentrated. The resulting product can be
recrystallized from an alkanol, such as isopropanol, or the like, or a
ketone, such as 2-butanone, or the like, if desired.
(D) Toners And Toner Preparation
The quaternary ammonium salts of the present invention are incorporated
into toner particles: For present purposes, toner particles can be
regarded as being preferably comprised on a 100 weight percent basis of:
(a) about 0.5 to about 10 weight percent of at least one quaternary
ammonium salt;
(b) about 75 to about 97.5 weight percent of a thermoplastic polymer; and
(c) about 2 to about 15 weight percent of a colorant.
Toner particles in accordance with the present invention include a
thermoplastic polymeric matrix phase which has dispersed therein a
quaternary ammonium salt of the formula:
##STR5##
wherein R.sub.1 is alkyl, aryl, and
##STR6##
wherein R.sub.5 is arylene or alkylene; R.sub.2 is alkyl, aryl or aralkyl;
R.sub.3 is alkyl, aryl, aralkyl or
##STR7##
R.sub.4 is alkyl, aryl or aralkyl; X is (CH.sub.2).sub.n or arylene;
Z.sup..crclbar. is an anion; and
n is an integer from 2 to 6.
The size of the toner particles is believed to be relatively unimportant
from the standpoint of the present invention; rather the exact size and
size distribution is influenced by the end use application intended. So
far as now known, the toner particles of this invention can be used in all
known electrophotographic copying processes. Typically and illustratively,
toner particle sizes range from about 0.5 to about 100 microns, preferably
from about 4 to about 35 microns.
The properties of a thermoplastic polymer employed as a toner matrix phase
can vary widely. Typically and preferably, toner polymers have a glass
transition temperature in the range of about 50 to about 120.degree. C.
and a melting temperature in the range of about 65 to about 200.degree. C.
Preferably, such a polymer has a number average molecular weight in the
range of about 1,000 to about 500,000. The weight average molecular weight
can vary, but preferably is in the range of about 2,000 to about 10.sup.6.
Typical examples of such polymers include polystyrene, polyacrylates,
polyesters, polyamides, polyolefins, polycarbonates, phenol formaldehyde
condensates, alkyd resins, polyvinylidene chlorides, epoxy resins, various
copolymers of the monomers used to make these polymers, such as
polyesteramides, acrylonitrile copolymers with monomers, such as styrene,
acrylics, and the like.
Preferably, thermoplastic polymers used in the practice of this invention
are substantially amorphous. However, mixtures of polymers can be
employed, if desired, such as compatible mixtures of substantially
amorphous polymers with substantially crystalline polymers.
Presently preferred polymers for use in toner powders are polyesters. The
structure of the polyester polymer can vary widely, and mixtures of
different polyesters can be employed. Polyesters and methods for making
such are generally known to the prior art. One presently preferred
polyester is copoly(1,2-propylene:1,2,3-propanetriyl
terephthalate:glutarate) having an inherent viscosity in the range of
about 0.25 to about 0.35 in methylene chloride solution at a concentration
of about 0.25 grams of polymer per 100 milliliters of solution. In
general, preferred polyesters have a glass transition temperature
(T.sub.g) in the range of about 50.degree.to about 120.degree. C. and a
melting temperature (T.sub.m) in the range of about 65.degree.to about
200.degree. C.
An optional but preferred starting material for inclusion in such a blend
is a colorant (pigment or dye). Suitable dyes and pigments are disclosed,
for example, in U.S. Pat. No. Re. 31,072, and in U.S. Pat. Nos. 4,140,644;
4,416,965; 4,414,152; and 2,229,513. One particularly useful colorant for
the toners to be used in black and white electrophotographic copying
machines is carbon black. When employed, colorants are generally employed
in quantities in the range of about 1 to about 30 weight percent on a
total toner powder weight basis, and preferably in the range of about 1 to
about 8 weight percent.
The quaternary ammonium salts of the present invention are compatible with
conventional charge control agents and other toner additives. If desired,
a conventional charge control agent can be additionally incorporated into
a toner particle composition. Examples of such charge control agents for
toner usage are described in, for example, U.S. Pat. Nos. 3,893,935;
4,079,014; 4,323,634; and British Patent Nos. 1,501,065 and 1,420,839. If
used, charge control agents are preferably employed in small quantities,
such as an amount in the range of about 0.1 to about 5 weight percent on a
total toner composition weight basis, and preferably in the range of about
0.1 to about 3 weight percent.
Toner compositions, if desired, can also contain other additives of the
types which have been heretofore employed in toner powders, including
leveling agents, surfactants, stabilizers, and the like. The total
quantity of such additives can vary. A present preference is to employ not
more than about 10 weight percent of such additives on a total toner
powder composition weight basis.
Various procedures are known to the art for incorporating additives, such
as the quaternary ammonium salts of the present invention, colorants, or
the like, into a desired polymer. For example, a preformed mechanical
blend of particulate polymer particles, quaternary ammonium salts,
colorants, etc., can be roll milled or extruded at a temperature above
which the polymer is no longer glassy but is at least rubbery and can flow
in order to achieve a uniformly blended composition. Thereafter, the
cooled composition can be ground and classified, if desired, to achieve a
desired toner powder size and size distribution.
Preferably, prior to melt blending, the toner components, which preferably
are preliminarily placed in a particulate form, are blended together
mechanically. With a polymer having a T.sub.g or a T.sub.m within the
ranges above indicated, a melt blending temperature in the range of about
90.degree. to about 160.degree. C. is suitable using a roll mill or
extruder. Melt blending times (that is, the exposure period for melt
blending at elevated temperatures) are in the range of about 1 to about 60
minutes. After melt blending and cooling, the composition can be stored
before being ground. Grinding can be carried out by any convenient
procedure. For example, the solid composition can be crushed and then
ground using, for example, a fluid energy or jet mill, such as described
in U.S. Pat. No. 4,089,472. Classification, if employed, can be
conventionally accomplished using one or two steps.
In place of melt blending, the polymer can be dissolved in a solvent and
the additives dissolved and/or dispersed therein. Thereafter, the
resulting solution or dispersion can be spray dried to produce particulate
toner powders.
Limited coalescence polymer suspension procedures, are particularly useful
for producing small sized, uniform toner particles, such as toner
particles under about 10 microns in size.
Toner powders of this invention preferably have a fusing latitude
temperature in the range of about 275.degree. to about 400.degree. F.,
although toner powders with higher and lower fusing temperatures can be
prepared and used. Toner powders of this invention characteristically
display excellent paper adhesion characteristics. Typically, toner powders
of this invention have a paper adhesion index value in the range of about
30 to about 100, although toner powders with lower such values can be
prepared and used. Paper adhesion index values of toner powders of this
invention are characteristically higher than those of toner powders
prepared with the same polymer and additives but not containing a
quaternary ammonium salt of this invention.
When the polymer employed in a toner powder of this invention is a
polyester, the ester group containing quaternary ammonium salts used in
this invention display superior ester compatibility therewith.
To be utilized as toners in electrostatographic developers of the
invention, toners containing the aforedescribed salts can be mixed with a
carrier vehicle. The carrier vehicles which can be used to form such
developer compositions can be selected from a variety of materials. Such
materials include carrier core particles and core particles overcoated
with a thin layer of film-forming resin.
The carrier core materials can comprise conductive, non-conductive,
magnetic, or non-magnetic materials. For example, carrier cores can
comprise glass beads; crystals of inorganic salts such as aluminum
potassium chloride; other salts such as ammonium chloride or sodium
nitrate; granular zircon; granular silicon; silicon dioxide; hard resin
particles such as poly(methyl methacrylate); metallic materials such as
iron, steel, nickel, carborundum, cobalt, oxidized iron; or mixtures or
alloys of any of the foregoing. See, for example, U.S. Pat. Nos. 3,850,663
and 3,970,571. Especially useful in magnetic brush development schemes are
iron particles such as porous iron particles having oxidized surfaces,
steel particles, and other "hard" and "soft" ferromagnetic materials such
as gamma ferric oxides or ferrites, such as ferrites of barium, strontium,
lead, magnesium, or aluminum. See, for example, U.S. Pat. Nos. 4,042,518;
4,478,925; and 4,546,060.
As noted above, the carrier particles can be overcoated with a thin layer
of a film-forming resin for the purpose of establishing the correct
triboelectric relationship and charge level with the toner employed.
Examples of suitable resins are the polymers described in U.S. Pat. Nos.
3,547,822; 3,632,512; 3,795,618 and 3,898,170 and Belgian Pat. No.
797,132. Other useful resins are fluorocarbons such as
polytetrafluoroethylene, poly(vinylidene fluoride), mixtures of these, and
copolymers of vinylidene fluoride and tetrafluoroethylene. See, for
example, U.S. Pat. Nos. 4,545,060; 4,478,925; 4,076,857; and 3,970,571.
Such polymeric fluorohydrocarbon carrier coatings can serve a number of
known purposes. One such purpose can be to aid the developer to meet the
electrostatic force requirements mentioned above by shifting the carrier
particles to a position in the triboelectric series different from that of
the uncoated carrier core material, in order to adjust the degree of
triboelectric charging of both the carrier and toner particles. Another
purpose can be to reduce the frictional characteristics of the carrier
particles in order to improve developer flow properties. Still another
purpose can be to reduce the surface hardness of the carrier particles so
that they are less likely to break apart during use and less likely to
abrade surfaces (e.g., photoconductive element surfaces) that they contact
during use. Yet another purpose can be to reduce the tendency of toner
material or other developer additives to become undesirably permanently
adhered to carrier surfaces during developer use (often referred to as
scumming). A further purpose can be to alter the electrical resistance of
the carrier particles.
A typical developer composition containing the above-described toner and a
carrier vehicle generally comprises from about 1 to about 20 percent by
weight of particulate toner particles and from about 80 to about 99
percent by weight carrier particles. Usually, the carrier particles are
larger than the toner particles. Conventional carrier particles have a
particle size on the order of from about 20 to about 1200 microns,
preferably 30-300 microns.
Alternatively, the toners of the present invention can be used in a single
component developer, i.e., with no carrier particles.
The toner and developer compositions of this invention can be used in a
variety of ways to develop electrostatic charge patterns or latent images.
Such developable charge patterns can be prepared by a number of means and
be carried for example, on a light-sensitive photoconductive element or a
non-light-sensitive dielectric-surface element such as an insulator-coated
conductive sheet. One suitable development technique involves cascading
the developer composition across the electrostatic charge pattern, while
another technique involves applying toner particles from a magnetic brush.
This latter technique involves the use of a magnetically attractable
carrier vehicle in forming the developer composition. After imagewise
deposition of the toner particles, the image can be fixed, e.g., by
heating the toner to cause it to fuse to the substrate carrying the toner.
If desired, the unfused image can be transferred to a receiver such as a
blank sheet of copy paper and then fused to form a permanent image.
The invention is further illustrated by the following Examples. In these
Examples, all melting points and boiling points are uncorrected. NMR
(nuclear magnetic resonance) spectra were obtained with a Varian
Gemini-200 NMR spectrometer. All elemental analyses were performed by
combustion. Unless otherwise indicated, all starting chemicals were
commercially obtained.
EXAMPLE 1
2-(N,N-Dimethylamino)ethyl 4-methylvalerate
A solution of 67.31 g (0.50 mol) of 4-methylvaleryl chloride in 300 ml of
methylene chloride was added to a solution of 44.57 g (0.50 mol) of
2-dimethylaminoethanol, 20.0 g (0.50 mol) of sodium hydroxide and 300 ml
of water in a stream via a dropping funnel while maintaining rapid
stirring. The reaction was exothermic and was stirred for an additional 20
minutes. The organic layer was then separated, washed with water, dried
over MgSO.sub.4 and concentrated to an oil. Distillation of the oil gave
56.8 g of product; bp=70.degree. C./0.80 mm.
Anal. Calcd. for C.sub.10 H.sub.21 NO.sub.2 : C, 64.13; H, 11.30; N, 7.48
Found: C, 59.78; H, 10.94; N, 6.51.
EXAMPLE 2
2-(N,N-Dimethylamino)ethyl benzoate
A solution of 70.29 g (0.50 mol) of benzoyl chloride in 500 ml of methylene
chloride was added to a solution of 44.57 g (0.50 mol) of
2-dimethylaminoethanol, 20.0 g (0.50 mol) of sodium hydroxide and 500 ml
of water over 15 minutes with rapid stirring. Stirring was continued for
3.25 hours after which the organic layer was separated, washed with water,
dried over MgSO.sub.4 and concentrated. Distillation of the residue gave
59.5 g of product; bp=102.degree.-8.degree. C./0.50 mm.
Anal. Calcd. for C.sub.11 H.sub.15 NO.sub.2 : C, 68.37; H, 7.82; N, 7.25;
Found: C, 66.11; H, 7.89; N, 7.25
EXAMPLE 3
2-(N,N-Dimethylamino)ethyl 2-ethyl hexanoate
The title compound was prepared by the procedure of Example 1.
EXAMPLE 4
2-(N,N-Dimethylamino)ethyl cyclohexanoate
The title compound was prepared by the procedure of Example 1.
EXAMPLE 5
2-(N,N-Dimethylamino)ethyl myristate
A solution of 91.35 g (0.40 mol) of myristic acid, 35.7 g (0.40 mol) of
2-dimethylaminoethanol, 0.5 g of p-toluenesulfonic acid and a suitable
volume of toluene was heated at reflux for approximately 48 hours in a
1-neck 3 liter flask equipped with Dean-Stark trap and condenser. At the
end of this time, 7.0 ml of water had collected in the trap. The solution
was cooled, stirred with K.sub.2 CO.sub.3, filtered and concentrated. The
residue was distilled to give 75.0 g of product; bp=145.degree.-50.degree.
C./0.50 mm.
EXAMPLE 6
2-(N,N-Dimethylamino)ethyl 4-chlorobenzoate
The title compound was prepared by the procedure of Example 1.
EXAMPLE 7
2-(N,N-Dimethylamino)ethyl 4-methoxybenzoate
The title compound was prepared by the procedure of Example 1.
The acid or acid chloride starting materials and the analytical data for
the ester products are shown in Table I below for Examples 1-7.
TABLE I
__________________________________________________________________________
2-(N,N-DIMETHYLAMINO)ETHYL ESTERS
Analysis
Ex.
Starting Acid Or Calcd Found
No.
Acid Chloride
Identity of R.sub.1
bp, C/mm
C H N Cl C H N Cl
__________________________________________________________________________
1 4-methylvaleroyl
(CH.sub.3).sub.2 CHCH.sub.2 CH.sub.2
70/0.8 64.13
11.30
7.48 59.78
10.94
6.51
chloride
2 benzyl chloride
##STR8## 102-8/0.5
68.37
7.82
7.25 66.11
7.89
7.25
3 2-ethyl hexanoyl
CH.sub.3 (CH.sub.2).sub.3 CH(C.sub.2 H.sub.5)
75-8/0.75
66.9
11.7
6.5 65.4
10.8
6.3
chloride
4 cyclohexane- carbonyl chloride
##STR9## 88-9/0.40.sup.(1)
66.29
10.62
7.03 66.38
10.99
7.49
5 myristic acid
CH.sub.3 (CH.sub.2).sub.12
145-50/0.5
72.19
12.45
4.68 72.34
12.06
3.98
6 4-chlorobenzoyl chloride
##STR10## 122-8/0.50
58.03
6.20
6.15
15.57
57.50
6.29
6.04
14.84
7 4-methoxy benzoyl chloride
##STR11## 128-40/0.30
64.55
7.67
6.27 64.59
7.46
6.13
__________________________________________________________________________
.sup.(1) intermediate ester distilled twice before analysis
EXAMPLE 8
N-(2-(4-Methylvaleryloxy)ethyl)-N,N-dimethylbenzylammonium chloride
A solution of 46.83 g (0.25 mol) of 2-(N,N-dimethylamino)ethyl
4-methylvalerate (prepared as described in Example 1) and 31.65 g (0.25
mol) of benzyl chloride in 250 ml of acetonitrile was heated at reflux for
1.25 hours. The reaction mixture was then concentrated to a viscous oil
and used in the ion exchange step with no further purification.
EXAMPLE 9
N-(2-(Benzoyloxy)ethyl)-N,N-dimethylbenzylammonium chloride
A solution of 57.96 g (0.30 mol) of 2-(N,N-dimethylamino)ethyl benzoate
(prepared as described in Example 2), 37.98 g (0.30 mol) of benzyl
chloride and 500 ml of acetonitrile was heated at reflux for 2 hours. The
reaction mixture was concentrated to a white solid which was then washed
with ether and recrystallized from acetonitrile. The yield of product was
69.0 g; mp=164.degree.-6.degree. C.
EXAMPLE 10
N-(2-(2-Ethylhexanoyloxy)ethyl)-N,N-dimethylbenzylammonium chloride
The title compound was prepared by the procedure of Example 8.
EXAMPLE 11
N-(2-(Cyclohexanoyloxy)ethyl)-N,N-dimethylbenzylammonium chloride
The title compound was prepared by the procedure of Example 8
EXAMPLE 12
N-(2-(Myristyloxy)ethyl)-N,N-dimethylbenzylammonium chloride
The title compound was prepared by the procedure of Example 8.
EXAMPLE 13
N-(2-(4-Chlorobenzoyloxyl)ethyl)-N,N-dimethylbenzylammonium chloride
The title compound was prepared by the procedure of Example 9.
EXAMPLE 14
N-(2-(4-Methoxybenzoyloxy)ethyl)-N,N-dimethylbenzylammonium chloride
The title compound was prepared by the procedure of Example 9.
The ester starting materials and the analytical data for the quaternary
ammonium chloride products are shown in Table II below for Examples 8-14.
TABLE II
__________________________________________________________________________
N-(2-ACYLOXYETHYL)-N,N-DIMETHYLBENZYLAMMONIUM CHLORIDES*
##STR12##
Analysis
Ex.
Starting Calcd Found
No.
Ester
Identity of R.sub.1
mp, C.
C H N Cl C H N Cl
__________________________________________________________________________
8 1 (CH.sub.3).sub.2 CHCH.sub.2 CH.sub.2
oil
9 2
##STR13## 164-6
67.6
6.9
4.4
11.1
66.6
6.9
4.3
11.2
10 3 CH.sub.3 (CH.sub.2).sub.3 CH(C.sub.2 H.sub.5)
oil
11 4
##STR14## oil
12 5 CH.sub.3 (CH.sub.2).sub.12
oil
13 6
##STR15## 196 dec
61.03
5.97
3.95
20.01
60.63
5.86
4.02
20.05
14 7
##STR16## 195-6 dec
65.23
6.91
4.00
10.13
64.97
6.77
4.13
11.43
__________________________________________________________________________
*Quaternizing agent was benzyl chloride
EXAMPLE 15
N-(2-(4-Methylvaleryloxy)ethyl)-N,N-dimethylbenzylammonium
m-nitrobenzenesulfonate
A hot solution (300 ml) of 56.29 g (0.25 mol) of sodium
m-nitrobenzenesulfonate in water was added to a solution (300 ml) of 78.48
g (0.25 mol) of N-(2-(4-methylvaleryloxy)ethyl)-N,N-dimethylbenzylammonium
chloride (prepared as described in Example 8) in water. An oily
precipitate formed immediately which crystallized on cooling. The solid
was collected, washed with water and dissolved in methylene chloride. The
water layer was separated and the organic layer was dried over MgSO.sub.4
and concentrated. Recrystallization of the solid residue from isopropanol
gave 81.6 g of product; mp=106.degree.-8.degree. C.
Anal. Calcd. for C.sub.23 H.sub.32 N.sub.2 O.sub.7 S: C, 57.84; H, 6.71; N,
5.83; S, 6.67 Found: C, 57.26; H, 6.53; N, 5.90; S, 6.85.
EXAMPLE 16
N-(2-(Benzoyloxy)ethyl)-N,N-dimethylbenzylammonium m-nitrobenzenesulfonate
A solution of 45.03 g (0.20 mol) of sodium m-nitrobenzenesulfonate in 200
ml of water was added to a solution of 63.97 g (0.20 mol) of
N-(2-(benzoyloxy)ethyl)-N,N-dimethylbenzylammonium chloride (prepared as
described in Example 9) in 250 ml of water. An oily precipitate
immediately formed. The water was decanted from the oil and fresh water
was added. After standing overnight, the oil was taken up in methylene
chloride. The water layer was separated and the organic layer was dried
over MgSO.sub.4 and concentrated to an oil which crystallized on treatment
with ether. The solid was collected, recrystallized from 2-butanone,
collected, washed with ether and dried. The yield of product was 36.0 g;
mp=104.degree.-6.degree. C.
Anal. Calcd for C.sub.24 H.sub.26 N.sub.2 O.sub.7 S: C, 59.25; H, 5.39; N,
5.76; S, 6.59 Found: C, 58.90; H, 5.34; N, 5.62; S, 6.76.
EXAMPLE 17
N-(2-(2-Ethylhexanoyloxy)ethyl)-N,N-dimethylbenzylammonium
m-nitrobenzenesulfonate
The title compound was prepared by the procedure of Example 16.
EXAMPLE 18
N-(2-(Cyclohexanoyloxy)ethyl)-N,N-dimethylbenzylammonium
m-nitrobenzenesulfonate
The title compound was prepared by the procedure of Example 16.
EXAMPLE 19
N-(2-(Myristyloxy)ethyl)-N,N-dimethylbenzylammonium m-nitrobenzenesulfonate
The title compound was prepared by the procedure of Example 16.
EXAMPLE 20
N-(2-(4-Chlorobenzoyloxy)ethyl)-N,N-dimethylbenzylammonium
m-nitrobenzenesulfonate
The title compound was prepared by the procedure of Example 16.
EXAMPLE 21
N-(2-(4-Methoxybenzoyloxy)ethyl)-N,N-dimethylbenzylammonium
m-nitrobenzenesulfonate
The title compound was prepared by the procedure of Example 16.
The quaternary ammonium chloride starting materials and the analytical data
for the quaternary ammonium m-nitrobenzenesulfonate salt products are
shown in Table III below for Examples 15-21.
TABLE III
__________________________________________________________________________
N-(2-ACYLOXYETHYL)-N,N-DIMETHYLBENZYLAMMONIUM m-NITROBENZENESULFONATES*
##STR17##
Analysis
Ex.
Starting Calcd Found
No.
Chloride
Identity of R.sub.1
mp, C C H N Cl S C H N Cl S
__________________________________________________________________________
15 8 (CH.sub.3).sub.2 CHCH.sub.2 CH.sub.2
106-8 57.48
6.71
5.83 6.67
57.26
6.53
5.90 6.85
16 9
##STR18## 104-6 59.25
5.39
5.76 6.59
58.90
5.34
5.62 6.76
17 10 CH.sub.3 (CH.sub.2).sub.3 CH(C.sub.2 H.sub.5)
-- 59.04
7.13
5.51 6.30
59.32
7.02
5.48 6.31
18 11
##STR19## 97-9 58.5
6.54
6.51 6.51
58.5
6.39
6.58 6.58
19 12 CH.sub.3 (CH.sub.2).sub.12
54-7 62.81
8.16
4.73 5.41
63.27
8.36
4.09 4.54
20 13
##STR20## 123.5-125.5
55.33
4.84
5.38
6.80
6.15
55.45
4.87
5.20
7.39
6.30
21 14
##STR21## 152-153
58.13
5.46
5.42 6.21
58.18
5.56
5.42 6.71
__________________________________________________________________________
*low exchange agent was sodium mnitrobenzenesulfonate
EXAMPLE 22
N,N-Bis(2-(Cyclohexanoyloxy)ethyl)methylamine
A solution of 73.31 g (0.50 mol) cyclohexanecarbonyl chloride in 200 ml of
methylene chloride was added to a solution of 29.79 g (0.25 mol) of
N-methyldiethanolamine, 20.0 g (0.50 mol) of sodium hydroxide and 200 ml
of water over approximately 1 minute. The reaction was exothermic
requiring the use of a reflux condenser. The reaction mixture was stirred
for another 45 minutes after which the organic layer was separated, washed
with water, dried over MgSO.sub.4 and concentrated. The residue was
distilled to give product, bp=192.degree.-9.degree. C./0.30 mm.
Anal. Calcd for C.sub.19 H.sub.33 NO.sub.4 : C, 67.22; H, 9.80; N, 4.13
Found: C, 67.45; H, 10.05; N, 4.31.
EXAMPLE 23
N,N-Bis(2-(Cyclohexanoyloxy)ethyl)-N-methylbenzylammonium chloride
A solution of 28.5 g (0.084 mol) of
N,N-bis(2-(cyclohexanoyloxy)ethyl)methylamine (prepared as described in
Example 22), 10.63 g (0.084 mol) of benzyl chloride and 200 of
acetonitrile was heated at reflux for 2.5 hours and concentrated to an
oil. Ether was added to the oil which induced crystallization. The white
solid was collected, washed two times with ether and recrystallized from
2-butanone. The yield of product was 8.3 g; mp=143.5.degree.-4.5.degree.
C.
Anal. Calcd for C.sub.26 H.sub.40 ClNO.sub.4 : C, 67.01; H, 8.65; Cl, 7.61;
N, 3.01 Found: C, 66.86; H, 8.51; Cl, 7.51; N, 2.93.
EXAMPLE 24
N,N-Bis(2-(Cyclohexanoyloxy)ethyl)-N-methylbenzylammonium
m-nitrobenzenesulfonate
A solution of 3.38 g (0.015 mol) of sodium m-nitrobenzenesulfonate in 15 ml
of water was added to a solution of 7.0 g (0.015 mol) of
N,N-bis(2-(cyclohexanonyloxy)ethyl)-N-methylbenzylammonium chloride
(prepared as described in Example 23) in 50 ml of water. An oily
precipitate immediately formed. The oil was rinsed twice with water,
dissolved in methylene chloride, dried over MgSO.sub.4 and concentrated.
The resultant oil was crystallized with P-513 ligroine and warmed. The
crystals were collected, washed with ether, dried and recrystallized from
2-butanone. The yield of product was 2.64 g; mp=123.degree.-4.5.degree. C.
Anal. Calcd for C.sub.32 H.sub.44 N.sub.2 O.sub.9 S: C, 60.74; H, 7.01; N,
4.43; S, 5.07 Found: C, 60.37; H, 6.93; N, 4.34; S, 5.17.
EXAMPLE 25
Bis(2-dimethylaminoethyl) terephthalate
A solution of 40.60 g (0.20 mol) of terephthaloyl chloride in 20 ml
methylene chloride was gradually added to a solution of 35.66 g (0.40 mol)
of 2-dimethylaminoethanol, 16.0 g (0.40 mol) of sodium hydroxide and 200
ml of water and stirred rapidly. The reaction was exothermic and achieved
reflux. The mixture was stirred for another 1.75 hours after which the
organic layer was separated, washed with water, dried over MgSO.sub.4 and
concentrated to an oil.
Anal. Calcd for C.sub.16 H.sub.24 N.sub.2 O.sub.4 : C, 62.32; H, 7.84; N,
9.08 Found: C, 60.74; H, 8.56; N, 9.58.
EXAMPLE 26
Bis(2-(N,N-dimethylbenzylammonium)ethyl) terephthalate dichloride
A solution of 30.84 g (0.10 mol) of bis(2-dimethylaminoethyl) terephthalate
and 25.32 g (0.20 mol) of benzyl chloride was heated on a steam bath.
Within a few minutes, the mixture solidified. The resultant caked solid
was washed with acetonitrile and used in the next step without further
purification.
EXAMPLE 27
Bis(2-(N,N-dimethylbenzylammonium)ethyl) terephthalate
bis(m-nitrobenzenesulfonate)
A solution of 56.16 g (0.10 mol) of the crude
bis(2-(N,N-dimethylbenzylammonium)ethyl)terephthalate dichloride prepared
as described in Example 26 in 200 ml of water was added to a solution of
45.02 g (0.20 mol) of sodium m-nitrobenzenesulfonate in 200 ml of water.
An oily precipitate immediately formed. The aqueous phase was decanted and
the residue was washed several times with water. Ethyl acetate was added
to the oil and after standing the oil crystallized. The solid was
collected, washed with ether and recrystallized twice from acetonitrile to
give 32.7 g (36.5%) of a product whose melting point was
170.degree.-1.degree. C.
Anal. Calcd for C.sub.42 H.sub.46 N.sub.4 O.sub.14 S.sub.2 : C, 56.37; H,
5.18; N, 6.26; S, 7.17 Found: C, 56.13; H, 5.05; N, 6.21; S, 7.57.
EXAMPLE 28
Poly(2-dimethylaminoethyl methacrylate)
A solution of 50.0 g (0.318 mol) of N,N-dimethylaminoethyl methacrylate in
450 g of DMF was purged with nitrogen. Azobisisobutyronitrile (0.50 g) was
added and the solution was heated in a 60.degree. C. bath for 53.6 hours.
The resultant polymer was used in the next step without isolation.
EXAMPLE 29
Poly(2-(N,N-Dimethyl benzylammonium)ethyl methacrylate chloride)
The solution of poly(2-dimethylaminoethyl methacrylate) prepared in the
preceding Example 28 in dimethylformamide was treated with 40.26 g (0.318
mol) of benzyl chloride and heated under nitrogen in a 60.degree. C. bath
for 2 hours. A viscous oil precipitated and was allowed to stand for 10
days. Acetone was added to the mixture to harden the polymer which was
then collected and used in the next step with no further purification.
EXAMPLE 30
Poly(2-(N,N-Dimethylbenzyl ammonium)ethyl methacrylate
m-nitrobenzenesulfonate)
The poly(2-(N,N-dimethylbenzylammonium)ethyl methacrylate chloride)
prepared in the preceding Example 29 was dissolved in 1 liter of water and
to it was added a solution of 71.6 g (0.318 mol) of sodium
m-nitrobenzenesulfonate in 500 ml of water. A polymer immediately
precipitated. The aqueous phase was decanted and the polymer was allowed
to stand overnight in water. The water was decanted and the polymer was
washed with acetone and then ether, and finally dried. The polymer was
dissolved in DMF and reprecipitated into ether. The gummy precipitate was
isolated, washed again with ether and dried. The structure was confirmed
by NMR although the polymer was strongly contaminated with DMF.
EXAMPLES 31-33
The procedure for Example 16 is repeated except that, in place of sodium
m-nitrobenzenesulfonate, one equivalent of each of the ion exchange salts
shown in the following Table IV in such an aqueous solution is added to
the starting quaternary ammonium chloride solution. The structure of the
cation formed in, and the melting point of, each salt so recovered and
recrystallized is shown in Table IV. For comparison purposes, the melting
point of the product of Example 16, and the melting point of the starting
compound of Example 8 are included in Table IV.
TABLE IV
__________________________________________________________________________
N-(2-(BENZOYLOXY)ETHYL)-N,N-DIMETHYLBENZYLAMMONIUM
SALTS
##STR22##
Ex.
Starting Ion Exchange
No.
Agent Identity of Y.sup.- in Formula
Melting Point .degree.C.
__________________________________________________________________________
9 Cl.sup..crclbar.
164-6
16 sodium m-nitrobenzene- sulfonate
##STR23## 104-6
31 sodium tetraphenyl- borate
##STR24## 194-6
32 sodium dicyanamide
.sup..crclbar. N(CN).sub.2
(amorphous)
33 sodium p-toluenesulfonate
##STR25## 110-112
__________________________________________________________________________
EXAMPLE 34
2-Phenyl-1,3-dioxolane
A solution of 106.12 g (1.0 mol) of benzaldehyde, 74.48 g (1.2 mol) of
ethylene glycol, 500 ml of toluene and a catalytic amount of
p-toluenesulfonic acid was heated at reflux in a flask equipped with a
Dean-Stark trap for 1 hour and 25 minutes. The solution was cooled,
treated with K.sub.2 CO.sub.3, filtered, and distilled to yield 122.9 g of
product; bp=163.degree.-5.degree. C./mm.
EXAMPLE 35
2-Bromoethyl benzoate
A solution of 120.14 g (0.80 mol) of 2-phenyl-1,3-dioxolane, 142.39 g (0.80
ml) of N-bromosuccinimide, 1 liter of carbon tetrachloride, and a
catalytic amount of benzoyl peroxide was heated with stirring at reflux
for 51/4 hours and cooled in accordance with the method disclosed in J.
Org. Chem 43, 3418 (1978). The resulting mixture was filtered and the
filtrate was concentrated and distilled. 147.8 g of product was collected;
bp=104.degree.-111.degree. C./0.40 mm. (Rep. bp=90.degree.-2.degree.
C./0.5 mm.)
Anal.Calcd. for C.sub.9 H.sub.9 BrO.sub.2 : C, 47.19; H, 3.96 Found: C,
46.89; H, 4.24.
EXAMPLE 39
N-(2-(Benzoyloxy)ethyl)-N,N-dimethyl-n-octadecylammonium bromide
A mixture of 45.0 g (0.1964 mol) of 2-bromoethyl benzoate and an equimolar
amount of N,N-dimethyl-n-octadecylamine in 207 ml of acetonitrile was
heated at reflux for 4.5 hours. The reaction mixture was then cooled. The
solid was then collected, washed with ether, and dried to yield 76.7 g of
the title compound; mp=87.degree.-93.degree. C.
Anal.Calcd. for C.sub.29 H.sub.52 BrNO.sub.2 : C, 66.14; H, 9.95; N, 2.66
Found: C, 66.21; H, 9.69; N, 2.67.
EXAMPLE 37
N-(2-(Benzoyloxy)ethyl)-N,N-dimethyl-n-octadecylammonium
m-nitrobenzenesulfonate
To a solution of 26.33 g (0.05 mol) of
N-(2-(benzoyloxy)ethyl)-N,N-dimethyl-n-octadecylammonium bromide (prepared
as described in Example 36) dissolved in 500 ml of water at 70.degree. C.
was added a solution of 11.26 g (0.05 mol) of sodium
m-nitrobenzenesulfonate in 100 ml of water. The resultant mixture was
extracted with methylene chloride. The water layer was separated and the
organic layer was dried over MgSO.sub.4 and concentrated. The solid was
recrystallized from ethyl acetate, collected, washed with ligroine, and
dried to yield 21.7 g of the title compound; mp=80.degree.-3.degree. C.
##STR26##
Anal.Calcd. for C.sub.35 H.sub.56 N.sub.2 O.sub.7 S: C, 8.70; N, 4.32; S,
4.94; Found: C, 64.61; H, 8.85; N, 4.19; S, 4.67.
EXAMPLE 38
N-(2-(Benzoyloxy)ethyl)-N,N-dimethyl-n-octadecylammonium tetraphenylborate
The title compound was prepared by the procedure of Example 37 except that
an equimolar amount of sodium tetraphenylborate was used instead of sodium
m-nitrobenzenesulfonate to yield the title compound;
mp=110.degree.-17.degree. C.
##STR27##
Anal.Calcd. for C.sub.53 H.sub.72 BNO.sub.2 : C, 83.11; H, 9.47; B, 1.41;
N, 1.83; Found: C, 83.06; H, 9.75; B, 1.28; N, 1.89.
EXAMPLE 39
N,N-Bis(2-(Benzoyloxy)ethyl)-N,N-dimethylammonium bromide
Equimolar amounts of 2-bromoethyl benzoate (45.8 g) and
2-(N,N-dimethylamino)ethyl benzoate (38.5 g) were dissolved in 170 ml of
acetonitrile and heated at reflux for 16 hours. The reaction mixture was
then cooled and the resultant solid was collected, washed with ether, and
dried to yield 62.4 g of the title compound, mp=169.degree.-70.degree. C.
Anal. Calcd. for C.sub.20 H.sub.24 BrNO.sub.4 : C, 56.88; H, 5.73; N, 3.32;
Found: C, 56.49; H, 5.68; N, 3.38.
EXAMPLE 40
N,N-Bis(2-(Benzoyloxy)ethyl)-N,N-dimethylammonium m-nitrobenzenesulfonate
The title compound was prepared by the procedure of Example 37 except that
29.56 g (0.07 mol) of N,N-bis(2-benzoyloxy)ethyl)-N,N-dimethylammonium
bromide was used in place of
N-(2-(benzoyloxy)ethyl)-N,N-dimethyl-n-octadecylammonium bromide with an
equimolar amount of sodium m-nitrobenzenesulfonate to yield 26.8 g of the
title compound, mp=176.degree.-9.degree. C.
##STR28##
Anal. Calcd. for C.sub.26 H.sub.28 N.sub.2 O.sub.9 S: C, 57.34; H, 5.18; N,
5.14; S, 5.89; Found: C, 57.02; H, 5.18; N, 5.10; S, 6.30.
In a like manner, the tetraphenylborate analog, mp=194.degree.-5.degree. C.
can be prepared using the product of Example 39 and sodium
tetraphenylborate.
Anal. Calcd. for C.sub.44 H.sub.44 BNO.sub.4 : C, 79.87; H, 6.70; B, 1.63;
N, 2.12; Found: C, 79.76; H, 6.69; B, 1.71; N, 2.21.
EXAMPLE 41
Bis(2-(N,N-Dimethyl 2-(benzoyloxy)-ethylammonium)ethyl) terephthalate
bis(m-nitrobenzenesulfonate)
A solution of 34.2 g (0.1109 mol) of
bis(2-dimethylaminoethyl)terephthalate, 50.81 g (0.2218 mol) of
2-bromethyl benzoate and 170 ml of CH.sub.3 CN was heated at reflux until
solid began to form. Steam bath heating was continued with stirring for
15.7 hours, followed by cooling and collection of the solid. The solid was
washed with CH.sub.3 CN and dried to yield 74.8 g of the bromide
precursor, mp=221.degree.-2.degree. C. The title compound, mp
160.degree.-2.degree. C. was then prepared by the procedure of Example 37.
##STR29##
Anal. Calcd. for C.sub.46 H.sub.50 N.sub.4 O.sub.18 S.sub.2 : C, 54.65; H,
4.98; N, 5.5; S, 6.34; Found: C, 53.80; H, 4.78; N, 5.5; S, 6.44.
Similarly, the tetraphenylborate analog of Example 41 was prepared from
sodium tetraphenylborate and the bromide of Example 41.
Anal. Calcd. for C.sub.82 H.sub.82 B.sub.2 N.sub.2 O.sub.8 : C, 79.10; H,
6.64; N, 2.25; B, 1.74; Found: C, 78.29; H, 6.65; N, 2.22; B, 1.37.
EXAMPLE 42
N-(2-(Acetloxy)ethyl)-N,N,N-trimethylammonium tetraphenylborate
The title compound, mp=185.degree.-6.degree. C. was prepared by the
procedure of Example 37 from acetylcholine chloride and sodium
tetraphenylborate.
##STR30##
Anal.Calcd. for C.sub.31 H.sub.36 BNO.sub.2 : C, 80.00; H, 7.80; N, 3.01;
B, 2.32; Found: C, 80.20; H, 7.69; N, 3.00; B, 2.45.
EXAMPLE 43
N-(2-(Benzoyloxy)ethyl)-N,N-dimethyl (n-tetradecyl) ammonium
tetraphenylborate
A mixture of 40.0 g (0.1443 mol) of bromotetradecane, 27.87 g (0.1443 mol)
of N,N-dimethylaminoethyl benzoate and 135 ml CH.sub.3 CN was heated at
reflux for four hours and cooled. On standing, white solid crystallized.
The solid was collected. Washed with a small amount of CH.sub.3 CN and
then with ether and dried to yield 48.4 g; mp=90.degree.-2.degree. C. of
the bromide precurser.
The bromide precursor was used to prepare the title compound,
mp=110.degree.-16.degree. C., by the procedure of Example 37 with sodium
tetraphenylborate.
##STR31##
Anal.Calcd. for C.sub.49 H.sub.64 BNO.sub.2 : C, 82.91; H, 9.09; N, 1.97;
B, 1.52; Found: C, 82.63; H, 9.02; N, 2.08, B, 1.51.
In a similar manner, the m-nitrobenzenesulfonate analog was prepared from
sodium m-nitrobenzenesulfonate; mp=85.degree.-7.degree. C.
Anal.Calcd. for C.sub.41 H.sub.48 N.sub.2 O.sub.7 S: C, 62.81; H, 8.16; N,
4.73; S, 5.41; Found: C, 62.50; H, 8.05; N, 4.65; S, 6.07.
EXAMPLES 44-46
Toner Powder Preparation
An amorphous branched polyester comprised of a condensate of
dimethylterephthalate (87 mol), dimethyl glutarate (13 mol),
1,2-propanediol (92.5 mol) and glycerol (5 mol) having a T.sub.g of
63.degree. C. and a number average molecular weight of about 12,000 was
prepared using a conventional polycondensation technique. This polymer was
preliminarily ground into particles having a size in the range of about
1/16", and such particles are blended with various additives as
individually identified in the following Table V to produce various blends
as shown in such Table.
TABLE V
__________________________________________________________________________
Toner Composition (Dry Weight Basis)
Component Blend Ex. 44
Blend Ex. 45
Blend Ex. 46
ID No.
Component wt %.sup.5
pph.sup.6
wt %.sup.5
pph.sup.6
wt %.sup.5
pph.sup.6
__________________________________________________________________________
1 Polyester 90.66
100.0
91.74
100.0
90.66
100.0
2 Carbon Black.sup.3
4.53
5.0 4.59
5.0 4.53
5.0
3 LSA.sup.4 3.63
4.0 3.67
4.0 3.63
4.0
4 Charge Control Agent
1.18.sup.1
1.3.sup.1
(none)
(none)
1.18.sup.2
1.3.sup.2
TOTAL 100 110.3
100 109.0
100 110.3
__________________________________________________________________________
Table V Footnotes:
.sup.1 Charge Control Agent
##STR32##
##STR33##
.sup.2 The charge control agent was the compound identified in Example 16
above.
.sup.3 The carbon black was "Regal .TM. 300" obtained commercially from
Cabot Corporation.
.sup.4 The LSA was a polyester/polydimethylsiloxane block copolymer as
described in U.S. Pat. No. 4,758,491.
.sup.5 Weight percent of a total blend composition basis.
.sup.6 Parts by weight.
Each blend was roll milled at 130.degree. C. for 12 minutes, cooled,
crushed, ground and classified to produce a toner powder product having a
size of about 12 microns and a size distribution of about 2-30 microns.
EXAMPLES 47-51
Toner Powder Preparation
The polyester used in preparing the toner compositions of Examples 44-46
was additionally compounded with various additives as individually
identified in the following Table VI.
TABLE VI
______________________________________
Toner Composition
Relative Parts, Dry Weight Basis
Com-
ponent Example No.
ID. No.
Component 47 48 49 50 51
______________________________________
1 polyester 100 100 100 100 100
2 carbon 5 5 5 5 5
black
3 LSA 2 2 2 2 2
4 Charge 1.50.sup.A
0.75.sup.B
1.50.sup.B
2.25.sup.B
1.50.sup.C
Control
Agent
______________________________________
Note:
.sup.A Charge control agent from Example 44
.sup.B Charge control agent from Example 18
.sup.C Charge control agent from Example 16
The carbon black was "Regal.TM. 300" as in Examples 44-46. The LSA was the
same as in Examples 44-46. The charge control agent used for the
formulation of Example 47 was the same as used in Example 44. The charge
control agent used in each of formulation Examples 48, 49, and 50 was the
compound identified in Example 18 above. The charge control agent used in
formulation of Examples 51 was the compound identified in Example 16
above. The charge control agent of formulation Example 47 was utilized for
comparative purposes.
Each of such five formulations was extruded in a twin screw corotating
extender.
The product so extruded was cooled, crushed, ground to produce toner
powders each having a size of about 12 microns and a size distribution of
about 2-30 microns.
EXAMPLE 52
(Comparative) Toner Powder Preparation
Using a polyester such as described in Examples 44-46, the following
formulation was compounded.
TABLE VII
______________________________________
Toner Composition (Dry Weight Basis)
Component Concentration
ID. No. Component pph
______________________________________
1 polyester 100
2 carbon black 5
3 Charge Control Agent
1.5
______________________________________
The carbon black was "Regal.TM. 300" as in Examples 44-46. The charge
control agent was methyltriphenyl phosphonium tosylate.
This blend was extruded on a twin screw extruder cooled, crushed, ground
and classified to produce a toner powder.
EXAMPLES 53-54
Toner Powder Preparation
The polyester described in Examples 44-46 was additionally compounded with
various additives as individually identified in the following Table VIII.
TABLE VIII
______________________________________
Toner Composition (Dry Weight Basis)
Blend Comp.
Blend Comp.
Component Ex. 53 Ex. 54
ID. No. Component pph pph
______________________________________
1 polyester 100 100
2 yellow pigment 3 3
3 Charge control agent
A 1.5
B 1.5
______________________________________
Charge control agent A was that used in Example 44; this charge control
agent and the formulation of Example 54 were utilized for comparative
purposes. Charge control agent B was the compound identified in Example 16
above.
Each blend was roll milled on the same roll mill as used in Examples 44-46,
cooled, crushed, ground and classified to produce a toner powder product.
EXAMPLES 55-58
Toner Powder Preparation
A styrene/butyl acrylate copolymer was obtained by limited coalescence
polymerization and blended with various additives as identified in the
following TABLE IX.
TABLE IX
______________________________________
Toner Composition
Relative Parts, Dry Weight Basis
Component Example No.
ID No. Component 55 56 57 58
______________________________________
1 Styrene/n-butyl
100 100 100 100
acrylate
copolymer
2 Carbon black
3 3 3 3
3 Charge Control
1.sup.A
1.sup.B
1.sup.C
1.sup.D
Agent
______________________________________
Note:
.sup.A Charge control agent from Example 44
.sup.B Charge control agent from Example 18
.sup.C Charge control agent from Example 18
.sup.D Charge control agent from Example 16
The carbon black was "Regal.TM. 300" as in Examples 44-46. The charge
control agent used for the formulation of Example 55 was as in Example 44.
The formulation of Example 55 was utilized for comparative purposes. The
charge control agent used for the formulation of Examples 56 and 57 was
the compound identified in Example 18 above. The charge control agent used
for the formulation of Example 58 was the compound identified in Example
16 above.
Each of such formulations was roll milled, cooled, crushed, ground and
classified to produce a toner powder product.
EXAMPLE 59
Toner T.sub.g
To determine if the quaternary ammonium salt compounds were plasticizing
the toner and thereby affecting fusing, the T.sub.g of each of the toner
powders of Examples 47-51 above was measured. The results were shown in
the following Table X.
TABLE X
______________________________________
Toner Glass Transition Temperature
Toner ID
T.sub.g
Ex. No. (.degree.C.)
______________________________________
47 60.6
48 62.2
49 61.8
50 60.9
51 60.8
______________________________________
Since this data shows that the toner powders containing the compounds of
Examples 16 and 18 had T.sub.g values which were equivalent to or slightly
above, the T.sub.g value for a toner powder containing the charge agent of
Example 44, it was concluded that the quaternary ammonium salt compounds
are not acting as plasticizers in toner particles.
EXAMPLE 60
Fusing And Adhesion
Each of the polyester-based toner powders of Examples 44-46 was evaluated
on a fusing breadboard consisting of a fusing roller coated with a
fluorocarbon elastomer (available commercially under the designation
Viton.TM. from E. I. du Pont de Nemours & Co.) engaged at constant speed
and pressure onto a backup roller coated with a polytetrafluorethylene
(available commercially as Silverstone.TM. from E. I. duPont de Nemours &
Co. Both rollers had their circumferential surfaces were coated by hand
using a release oil (available commercially under the designation "DC200
oil" from Dow Corning Company).
Six longitudinally extending stripes of toner were applied to various
receiver sheets which were then run through the fusing breadboard.
The receiver sheets were:
(a) Husky.TM. paper, an acidic paper, available commercially from
Weyerhauser Company;
(b) Kodak.TM. DP paper, available commercially from Eastman Kodak Company;
and
(c) Hammermill.TM. 9000 DP, an alkaline paper available commercially from
the Hammermill Company.
The adhesion index (A.I.) and crack width at various temperatures for each
toner powder were determined and used as an indication of fusing
performance. The results are shown for the Hammermill.
TABLE XI
______________________________________
Adhesion Index at Various Temperatures
Temperature Adhesion Index (AI) of Toner
.degree.F. Ex. 45 Ex. 44 Ex. 46
______________________________________
275 10 5 10
300 5 10 20
325 30 12 35
350 62 30 80
375 100 25 100
______________________________________
The toner of example 45 contained no charge agent and the toner of Example
51 contained the charge agent of the invention identified in Example 16.
The toner of Example 44 (comparative) reached the minimum acceptable
adhesion index (A.I.) value of 30 at 350.degree. F. The toner of Example
45 (which contained no charge agent), and the toner of Example 46
containing the quaternary ammonium salt of Example 16 reached the minimum
A.I. value at 325.degree. and 315.degree. F., respectively. The A.I.
values are the average of 3 measurements and the standard deviation of the
values is 10 A.I. units.
EXAMPLE 61
Fusing And Adhesion
Each of the styrene/n-butyl acrylate-based toner powders of Examples 55-58
was evaluated on a fusing breadboard similarly to the procedure described
in Example 60 except that the fusing roller was a Silverstone roller and
the backup roller was a red rubber roller. No wicking oil was applied to
the rollers.
The toner powders of Examples 55-58 reached the minimum A.I. of 30 at
365.degree., 320.degree., 310.degree., and 310.degree. F., respectively
(same standard deviation as in Example 60).
The average transmission density was between 0.8 and 1.2.
EXAMPLE 62
Crack And Rub
The crack and rub characteristics of the polyester based toners of Examples
44, 45, and 46 were evaluated and the results are as shown in Table XIII
below:
TABLE XII
______________________________________
Crack and Rub Analysis
Ref. Toner ID
No. Ex. No. 275.degree. F.
300.degree. F.
325.degree. F.
350.degree. F.
375.degree. F.
______________________________________
A Example 45
poor- poor- poor+ fair- good
B Example 44
poor- poor poor poor+ fair
C Example 46
poor- poor- poor+ good- good
______________________________________
The toner powder of Ex. 45 (no charge agent) was comparable to the toner
powder of Example 46 (containing the charge agent of Example 16), and they
both had acceptable crack and rub performance at a lower temperature than
the toner powder of Example 44.
EXAMPLE 63
Fusing And Adhesion
Each of the polyester based toner powders of Examples 47-52 was evaluated
for fusing and adhesion performance using "Husky.TM." paper and the
procedure of Example 60. The toner powder of Example 52 was included for
comparison purposes.
The adhesion index (A.I.) at various temperatures for each toner powder is
shown in Table XIII below.
TABLE XIII
______________________________________
Adhesion Index At Various Temperatures
Temperature
Adhesion Index (A.I.) of Toner
.degree.F.
Ex. 47 Ex. 48 Ex. 49
Ex. 50
Ex. 51
Ex. 52
______________________________________
325 21 38 20 21 23 14
350 21 40 35 46 62 50
375 25 83 100 83 100 100
______________________________________
In Table XIII, the values shown are the average adhesion index value of
three stripes and the standard deviation of the A.I. measurements was
between 0 and 10 units.
EXAMPLE 64
Crack and Rub
The procedure of Example 63 was repeated except that each of the polyester
based toner powders of Examples 47-51 was evaluated using "Hammermill.TM.
9000 DP" alkaline paper. The results are shown in Table XIV below.
TABLE XIV
______________________________________
Crack and Rub Analysis
Ref. Toner ID
No. Ex. No. Comment 325.degree. F.
350.degree. F.
375.degree. F.
400.degree. F.
______________________________________
A 47 poor poor poor fair-
B 48 poor poor fair no data
C 49 poor poor fair- fair+
D 50 poor fair- fair- good
E 51 poor fair fair good
______________________________________
EXAMPLE 65
Toner Powder Preparation (Dry Weight Basis)
A styrene/n-butyl acrylate copolymer was obtained by limited coalescence
polymerization and separately blended with each of the quaternary salt
charge control agents tabulated in Table XVI and with carbon black in the
following amounts:
TABLE XV
______________________________________
Component Parts By Weight
______________________________________
Styrene/n-butyl acrylate
100
Carbon black 6
Quaternary salt (charge control agent)
1
______________________________________
The carbon black was "Regal.TM. 300." Each blend was roll milled at
150.degree. C. for 20 minutes, cooled, crushed and classified to produce a
toner powder product having a size of about 12 microns and a size
distribution of about 2-30 microns.
EXAMPLE 66
Fusing and Adhesion Performance
Each of the styrene/n-butyl acrylate toner powders was evaluated on a
fusing breadboard consisting of a fusing roller coated with 100 mls of red
rubber, engaged at constant speed and pressure onto a backup roller coated
with polytetrafluoroethylene (available commercially as Silverstone.TM.
from E. I. duPont de Newmours and Co.). Both roller surfaces were coated
by hand with a release oil (60,000 centistoke polydimethylsiloxane oil
available from Dow Corning Co.). The nip width between the two rollers was
0.215-0.240 inch and the fuser was operated at 12 inches/second. The
fusing temperature was 350.degree. F.
Six longitudinally extending stripes of toner were applied to the wire side
of Kodak alkaline DP paper, and the toned papers were run through the
fusing breadboard. The transmission density of the toned, fused stripes
was between 1.2 and 1.5. The adhesion index was determined for each
stripe, and the results for each of the various toners are presented in
Table XVI. The adhesion index values are the average of 8 measurements and
the standard deviations are less than 7 units for the measurements.
TABLE XVI
______________________________________
Average
Example Adhesion
Blend Charge-Control Agent No. Index
______________________________________
A N,N-bis(2-(cyclohexanoyloxy)-
24 62
ethyl)-N-methyl-benzyl-ammonium
m-nitrobenzene-sulfonate
B Bis(2-(N,N-dimethyl benzyl-
27 75
ammonium)ethyl)terephthalate bis
(m-nitrobenzenesulfonate)
C N-(2-(benzoyloxy)ethyl-N,N-
31 68
dimethylbenzylammonium
tetraphenylborate
D N-(2-(benzoyloxy)ethyl)-N,N-
37 36
dimethyl-n-octadecylammonium
m-nitrobenzenesulfate
E N-(2-(benzoyloxy)ethyl)-N,N-
38 44
dimethyl-n-octadecylammonium
tetraphenylborate
F N,N-(2-(benzoyloxy)ethyl)-N,N-
40 69
dimethylammonium m-nitro-
benzenesulfonate
G Bis(2-(N,N-dimethy 2-(benzoyloxy)
41 75
ethylammonium)ethyl)/
terephthalate bis-(m-nitro-
benzenesulfonate)
H N-(2-(acetyloxy)ethyl)-N,N,N-tri-
42 64
methylammonium
tetraphenylborate
I N-(2-(benzoyloxy)ethyl)-N,N-
43 38
dimethyl (n-tetradecyl)ammonium
tetraphenylborate
______________________________________
The foregoing specification is intended as illustrative and is not to be
taken as limiting. Still other variations within the spirit and scope of
the invention are possible and will readily present themselves to those
skilled in the art.
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